This invention provides new compounds that are useful as insecticides and acaricides, new synthetic procedures and intermediates for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling insects and mites using the compounds.
There is an acute need for new insecticides and acaricides. Insects and mites are developing resistance to the insecticides and acaricides in current use. At least 400 species of arthropods are resistant to one or more insecticides. The development of resistance to some of the older insecticides, such as DDT, the carbamates, and the organophosphates, is well known. But resistance has even developed to some of the newer pyrethroid insecticides and acaricides. Therefore a need exists for new insecticides and acaricides, and particularly for compounds that have new or atypical modes of action.
A number of 3,5-diphenyl-1H-1,2,4-triazole derivatives have been described in the literature as having acaricidal activity. U.S. Pat. No. 5,482,951; JP 8092224, EP572142, JP 08283261. To applicants knowledge, however, none of these compounds has become a commercial product. Nitro furanyl triazoles are described by L. E. Benjamin and H. R. Snyder as antimicrobials (J. Heterocyclic Chem. 1976, 13, 1115) and by others as antibacterials (J. Med. Chem. 1973, 16(4), 312-319; J. Med. Chem. 1974, 17(7), 756-758). The present invention provides novel compounds with commercial level activity against mites and insects.
This invention provides novel substituted pyridyl triazole derivatives especially useful for the control of insects and mites.
More specifically, the invention provides novel insecticidally active compounds of the formula (1) 
wherein
Z is pyridyl, optionally substituted with up to four groups independently selected from the group consisting of Cl, F, methyl, halomethyl, methoxy, halomethoxy, and methylthio;
one of X and Y is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, alkoxyalkyl, phenyl, or substituted phenyl;
the other of X and Y is a group selected from 
xe2x80x83wherein
R2 is halo, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, or alkoxyalkyl;
R3 is selected from H, halo, lower alkyl, (C7-C21) straight chain alkyl, hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, haloalkenyl, CN, NO2, CO2R6, CON(R6)2, (C3-C6) cycloalkyl, S(O)mR6, SCN, pyridyl, pyridyloxy, substituted pyridyl, substituted pyridyloxy, phenoxy, substituted phenoxy, isoxazolyl, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, xe2x80x94(CH2)nR6, xe2x80x94CHxe2x95x90CHR6, xe2x80x94Cxe2x95x90CR6, xe2x80x94CH2OR6, xe2x80x94CH2SR6, xe2x80x94CH2NR6R6, xe2x80x94OCH2R6, xe2x80x94SCH2R6, xe2x80x94NR6CH2R6, xe2x80x94NCH3NH2, 
R4 and R5 are independently H, halo, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, NO2, CO2R6, CON(R6)2, or S(O)m alkyl, or
R4 and R5 form a 5 or 6 member saturated or unsaturated carbocyclic ring which may be substituted by 1 or 2 halo, lower alkyl, lower alkoxy or haloalkyl groups;
R6 is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl, or substituted phenyl;
m is 0, 1, or 2; and
n is 1 or 2;
p is an integer from 2 to 6;
or a phytologically acceptable acid addition salt or N-oxide thereof.
The priority document described compounds of the formula 
wherein
Z is 2-pyridyl, 3-pyridyl, or 4-pyridyl, optionally substituted with up to four groups independently selected from the group consisting of Cl, F, methyl, halomethyl, methoxy, and halomethoxy;
X is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, or alkoxyalkyl;
Y is a group selected from 
xe2x80x83wherein
R is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, or alkoxyalkyl;
R is selected from H, halo, lower alkyl, (C7-C21) straight chain alkyl, hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, haloalkenyl, CN, NO2, CO2R6, CON(R6)2, (C3-C6) cycloalkyl, S(O)mR6, SCN, pyridyl, substituted pyridyl, isoxazolyl, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, xe2x80x94(CH2)nR6, xe2x80x94CHxe2x95x90CHR6, xe2x80x94Cxe2x95x90CR6, xe2x80x94CH2OR6, xe2x80x94CH2SR6, xe2x80x94CH2NR6R6, xe2x80x94OCH2R6, xe2x80x94SCH2R6, xe2x80x94NR6CH2R6, 
R4 and R5 are independently H, halo, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO2R6, CON(R6)2, or S(O)m alkyl, or
R4 and R5 form a 5 or 6 member saturated or unsaturated carbocyclic ring which may be substituted by 1 or 2 halo, lower alkyl, lower alkoxy or haloalkyl groups;
R6 is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl, or substituted phenyl;
m is 0, 1, or 2; and
n is 1 or 2;
p is an integer from 2 to 6;
or a phytologically acceptable acid addition salt or N-oxide thereof.
Preferred compounds of formula (1) include the following classes:
(1) Compounds of formula (1) wherein wherein one of X and Y is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, substituted phenyl, or alkoxyalkyl; and the other of X and Y is optionally substituted phenyl, pyridyl, thienyl, cyclopropyl, or thiazolyl;
(2) Compounds of formula (1) wherein Z is a 4-pyridyl group optionally substituted with up to four groups independently selected from Cl, F, methyl, halomethyl, methylthio, methoxy, and halomethoxy.
(3) Compounds of class (2) wherein Z is a 4-pyridyl group of the formula 
xe2x80x83wherein R7 and R8 are independently H, Cl, F, methyl, halomethyl, methoxy, or halomethoxy.
(4) Compounds of class (3) wherein R7 and R8 are independently methyl, F or Cl.
(5) Compounds of class (4) wherein R7 and R8 are both F, where R7 is chloro and R8 is methyl, or where R7 is fluoro and R8 is methyl.
(6) Compounds of class (4) wherein R7 and R8 are both Cl.
(7) Compounds of formula (1), and particularly compounds of class (1), (2), (3), (4), (5), or (6) as defined above, wherein Y is a group of the formula 
xe2x80x83where R2, R3, R4, and R5 are as defined in formula (1)
(8) Compounds of formula (1), and particularly compounds of class (1), (2), (3), (4), (5), or (6) as defined above, wherein Y is a group of the formula 
xe2x80x83where R3, R4, and R5 are as defined in formula (1).
(9) Compounds of class (7) wherein Y is a group of the formula 
xe2x80x83where R3 is an electron withdrawing group such as Cl, Br, CF3 or NO2.
(10) Compounds of formula (1), and particularly compounds of class (1), (2), (3), (4), (5), or (6) as defined above, wherein Y is a group of the formula 
xe2x80x83where R3, R4, and R5 are as defined in formula (1).
(11) Compounds of formula (1), and particularly compounds of class (1), (2), (3), (4), (5), or (6) as defined above, wherein Y is a group of the formula 
xe2x80x83where R3, R4, and R5 are as defined in formula (1).
(12) Compounds of class (11) wherein R3, R4, and R5 are independently selected from H, halo, alkyl, and alkoxy.
(13) Compounds of class (12) wherein R3, R4, and R5 are independently selected from H, alkyl, and halo.
(14) Compounds of class (13) wherein R3, R4, and R5 are independently selected from H, methyl, Cl, and Br.
(15) Compounds of formula (1), and particularly compounds of class (1), (2), (3), (4), (5), or (6) as defined above, wherein Y is a group of the formula 
xe2x80x83where R3, R4, and R5 are as defined in formula (1).
(16) Compounds of formula (1) or any one of classes (1) through (15) wherein X is methyl.
The invention also provides new processes and intermediates for preparing compounds of formula (1) as well as new compositions and methods of use, which will be described in detail hereinafter.
Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated.
The term xe2x80x9clower alkylxe2x80x9d refers to (C1-C6) straight hydrocarbon chains and (C3-C6) branched and cyclic hydrocarbon groups.
The terms xe2x80x9clower alkenylxe2x80x9d and xe2x80x9clower alkynylxe2x80x9d refer to (C2-C6) straight hydrocarbon chains and (C3-C6) branched hydrocarbon groups containing at least one double or triple bond, respectively.
The term xe2x80x9clower alkoxyxe2x80x9d refers to xe2x80x94O-lower alkyl.
The terms xe2x80x9chalomethylxe2x80x9d, xe2x80x9chaloalkylxe2x80x9d, and xe2x80x9chaloalkenylxe2x80x9d refer to methyl, lower alkyl, and lower alkenyl groups substituted with one or more halo atoms.
The terms xe2x80x9chalomethoxyxe2x80x9d and xe2x80x9chaloalkoxyxe2x80x9d refer to methoxy and lower alkoxy groups substituted with one or more halo atoms.
The term xe2x80x9calkoxyalkylxe2x80x9d refers to a lower alkyl group substituted with a lower alkoxy group.
The term xe2x80x9calkoxyalkoxyxe2x80x9d refers to a lower alkoxy group substituted with a lower alkoxy group.
The terms xe2x80x9csubstituted naphthylxe2x80x9d, xe2x80x9csubstituted thienyl,xe2x80x9d xe2x80x9csubstituted pyrimidyl,xe2x80x9d xe2x80x9csubstituted pyrazolyl,xe2x80x9d xe2x80x9csubstituted pyridyl,xe2x80x9d and xe2x80x9csubstituted isoxaxolylxe2x80x9d refer to the ring system substituted with one or more groups independently selected from halo, halo (C1-C4) alkyl, CN, NO2, (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, (C1-C4) alkoxy, or halo (C1-C4) alkoxy.
The term xe2x80x9csubstituted phenylxe2x80x9d refers to a phenyl group substituted with one or more groups independently selected from halo, (C1-C10) alkyl, branched (C3-C6) alkyl, halo (C1-C7) alkyl, hydroxy (C1-C7) alkyl, (C1-C7) alkoxy, halo (C1-C7) alkoxy, phenoxy, phenyl, NO2, OH, CN, (C1-C4) alkanoyl, benzoyl, (C1-C4) alkanoyloxy, (C1-C4) alkoxycarbonyl, phenoxycarbonyl, or benzoyloxy.
The term xe2x80x9cpyridylxe2x80x9d refers to a 2-pyridyl, 3-pyridyl, or 4-pyridyl group.
Unless otherwise indicated, when it is stated that a group may be substituted with one or more substituents selected from an identified class, it is intended that the substituents may be independently selected from the class.
Compounds of formula (1) can be prepared by the methods described in U.S. Pat. Nos. 5,380,944 and 5,284,860 (Production Methods 1, 2 and 3). Additional methods will be described hereinafter.
Compounds of formula (1) wherein X is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, alkoxyalkyl, phenyl, or substituted phenyl; and Y is a group selected from 
can be prepared by the method illustrated in Scheme I: 
wherein X, Y and Z are as defined in formula (1) and R11 is lower alkyl, preferably methyl.
The starting material of formula (2) used in Scheme I can be prepared by reacting a amide of formula Zxe2x80x94CONH2 with phosphorus pentasulfide in pyridine at reflux.
In step a of Scheme I the compound of formula (2) is reacted with lower alkyl iodide, e.g. iodomethane, in acetone to provide a compound of formula (3). Acetone is the preferred solvent, however other polar aprotic solvents such as DMF or THF can be used.
In step b of Scheme I the compound of formula (3) is reacted with an acid chloride of formula Yxe2x80x94COCl in a nonreactive organic solvent such as benzene, toluene, xylenes, chloroform, dichloromethane, or 1,2-dichloroethane, at a temperature in the range from 0xc2x0 C. to the boiling point of the solvent.
In step c of Scheme I, the N-acylimidate of formula (4) is reacted with an N-methylhydrazine to provide the product of formula (1). The reaction is carried out in benzene, toluene, xylenes, chloroform, dichloromethane, or 1,2-dichloroethane, at a temperature in the range from 0xc2x0 C. to the boiling point of the solvent.
In another of its aspects, the invention provides novel intermediates of the formulas (2), (3), and (4) as defined above.